Process for treating petroleum emulsions



Patented rrnrlyrn nn encore, or s'r. LOUIS, am) wrano'n c. anaius, or tinrvnasrr'r" CITY, rais- MJISSOURI, A GOBPORATION OF MISSOURI.

SUURI, ASSIG-MORS TO WM. S. BARNICJTQ ('0 COMPANY, OF WEBSTER GROVES,

PROCESS FOR TREATING- ZPETROLEUM 'EME'ULSIONS.

lto Drawing.

This invention relatesto the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the water.

. t Petroleum emulsions of the kind referredo'treatment of petroleum emulsions to are commonly lmown as cut oil, roily oil, bottom settlings, etc., and consist of oil constituting the continuous phase of the emulsion, droplets of Water distributed throughout the body of oil and constituting the dispersed phase, and films of matter that encase the droplets of water. The conven tional process for breaking such emulsions contemplates subjecting the emulsion to the action of a substance or compound which acts on the emulsion in such a manner that the Water of the emulsion will separate from the oil when the emulsion is allowed to remain in a quiescent state at a suitable temperature after treatment. The pending aplication for patent of Melvin De Groote, erial No. 7 57 ,737, filed December 23,1924, describes 'a novel process for treating such emulsions to effect the, separation of the water from the oil, which consists in coating the walls of fissures in the films surroundin the droplets of water with a substance t at is capable of being wetted by water, thereby converting said fissures into an water passageways through which the drop lets of water in the films can escape, and thereafter coalesce. L

e We have discovered that proteins possess some of the characteristics that are essenaa tial' for a treating agent of the kinddescribed in said De Groote application, namel the ability to be wetted by water and ,t e

co sion and adsorb on thewa lls of fissures in the encasing; films, but proteins alone or unchanged cannot be used successfully, for breaking petroleum emulsions, on account of the fact that such material is so soluble that it will not remain on the Walls of the.

emulsion, or to be substantially insoluble or, K

. Therefore, we te1n condensation derivative'in which' the ability to disperse as a colloid; through the continuous phase of the emul ,Application filed dpril e, 1925. Serial no. 21,210.

tion with said alkaline earths.

We have found, however, that many tein derivatives are susceptible of use coarsely dispersed themselves without reacproin the v owing to the fact that theyv have the ability to be wetted by water and. to'adsorb strongly at interfacial surfaces andalso the ability to form insoluble salts of thealkaline earths. propose to iise a modified pros protein group bears a simple genetic relatlonship to the parent material as an-agent tiff to treat a petroleum emulsion to effect the separation of the oil and the water or brine.

The material condensed with the modified protein can be any material, such as a fatty acid, rosin, substance. The treating agent can be introduced into a producing well, it can be introduced into. a conduit through which a petroleum emulsion is flowing, or it can be ntroduced into a tank in which a petroleum emulsion or petroleum emulsion sludge is stored, thequantit of the treating agent that is required to break the emulsion depending upontthe nature and age of the einulsion and varying in ratio from 1 barrel, of treating agent to 2,000 barrels ofemulsion to 1 barrel of treating agent,to 20,000 barrels of emulsion. The treating agent can even be intronaphthenic acid or an aromatic duced into a' producing well in such a way that it will become mixed with water or oil that is emerging from the ground before said water and oil enter the barrel of-thewell pump, or the tubing up through which-said water and oil flow to the surface of the;

ground. ,After treatment the emulsion is allowed to stand in a quiescent state at a suitable temperature, so as'to permitthe water toseparate from the oil, or it may be passed through a' variety of apparatus, such as hay tanks, gun barrels, etc., such as are now commonly used in the operation of breaking emulsions. It'may even be passed through 'a centrifugal or an electrical dehydrator.

. A treating'agent of the kindraferr'ed to can be obtained by combining any suitable modified protein with an organic substance whose alkaline-earth salt is insoluble, the particular method that is employed to obtain the derivative being immaterial, so long as the resultant product may be said to consist of a derivative; obtained by the action of a the protein group bears a simple genetic rei anhydroxy fatty acid, 1i

tine,

*Glue is particularly adaptable for this purlationship to the parent material. We have found those protein derivatives most valuable that represent the condensation or addition products with some somewhat dissimilar material such as an aromatic compound or fatty acid. We have employed a number of methods for producing a treating agent/of the kind contemplated by our invention, suclras subjecting glue, which is aprotein, to the action of an acetylating agent in excess, and "subsequently adding thereto which is also acetylated, and combined with or condensed with glue. The resultant material is freedfrom excess acid and used in this state as a treating agent, or it can be saponified before'it is used. Or, if desired, said resultant material can be combined'with other materials of the kind now used to treat petroleum emulsions. Substantially the same procedure'can be followed in the case of a nitrating agent. .The glue is nitrated in the presence of an excess mtratin agent, and subsequently mixed with a atty material which is also nitrated. The resultant material is againv freed from excess acid and is then ready for use as a treating agent. We desire to point out that the action of well-known reagents such as acetylating agents, nitrating agents or sulphonating a ents alone on proteins produce compounds aving a mild treating action, but are vastly improved by combination with a dissimilar substance, as previously described. We prefer, however, to use the derivatives of proteins obtained by the action of sulphonating agents, and more specifically, y the action of commercial 66 sulphuric acid. Substantially any technically pure protein can be used in obtaining our improved treating agent, such as glue,-gelacasein, albumin, vegetable protein, etc.

po se because it is readily available at a low price, in a %ure form and in afinely powdered state, ut, as previously stated, our invention is not limited to a derivative obtained from any particular protein or to a protieni derivative obtained by the use of a sul honating agent;

t is obvious'that a chemical reaction of' the typewhich we are disclosing can be conducted in a variety of manners. We prefer to add one part'of the proteinv to fifteen parts of sulphuric acid, with constant stirring. The reaction should preferably not rise-about centigrade. WVhen all of the protein is dissolved, the resultant mass, after neutralization, can be used as atreating agent, but we prefer to unitethis glue 'derivative with other materialsor substances that endow it with more advantageous properties. Among such other materials or substances that we have found to be of considerits valuable able solution or suspension or are used T able value are poundsfwhich are susceptible to sulphonation, actylation or nitration. We have used such materials as phenol, naphthalene *or anthracene, ,etc., as .Well as the fatty materials, such as oleic acid, ricinoleic acid, eto. Rosin and the petroleum acids such as na hthenic' acids, are particularly desirablgdue to their low cost. Generally, we prefer to i added thereto 50 parts of the solution of protein prepared as previously directed. This reaction should take place below centigrade, and to that end the protein solution should not be added too quickly. The

resulting mass of sulphonation reaction is subsequently washed by means of water or sodium sulphate solution, or dilute ammonia water, or by any other-suitable means to remove the excess acid. The final material,

after being dried or partially or totally dehydrated is ready for use. The alkali salt' of this substance may be converted into the alkaline earth salt by double decomposition with calcium or magnesium chloride. It may be saponified or esterified, or treated in some other manner without detracting from roperties, We have found that castor oi handled substantially as described, gives an excellent treating agent, and this is the substance that" we prefer to use in connection with a derivative obtained from glue by means of sulphuric acid. It should be understobd, however, that the rotein derivative can be. combined with bot an aromatic and aliphatic compound. Moreover, more than one fatty acid can be used. For instance, a mixture of oleic acid and ricinoleic acid, or more. than one aromatlcsuch as napthalene or phenol may be used. We have described this general procedure so that one skilled inthe art can follow general chemical procedure in regard to chemical reactions, weights and preparewide varietypf protein having the above described tiesn I v p In treating petroleum emulsions with such materials, thematerials d 1 rectly without solution. In so fartl at some of said materials may be substantially insoluble inoil and water we prefer to mix tlfe aliphatic or aromatic com} are used in any 511113 them with agsuitable solubilizing agent.

Such solubilizing agent could be an agent that would give a dispersion of the sub iao stance in either water or oil, as the case may be, and COIIId COIISISt of ammonium oleate,

- calcium oleate, saponin, etc. The solubilizing agent needv only be mixed with the protein derivative and the amount of solubilizing agent used will be the minimum amount necessary to give a suitable dispersion ofjhe protein derivative.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is; 1

1. A process for treating petroleum emulsions, characterized by subjecting the emulsion to the action of a modified protein condensation derivative in which the protein 1 group bears a simple genetic relationship to the parent material.

2. A process for treating petroleum emulslons, characterized by subjecting the emulsion to the action of a modified protein con- 2 densation derivative in which the protein group bears a. simple genetic relationship to the parent material, and which contains an organic substance whose alkaline earth salt is insoluble.

MELVIN DE GROOTEI WILBUB o. ADAMS. 

